Printing



Patented Dec. 17, 1935 UNITED STATES PATENT OFFICE 2,024,974 rnm'mzo Herbert A..Lubs and mm Eltoncoi' 'wummton, Del, assignors to E. I. du Pont de Nemonrs a Company, Wilmington, DeL, a conventional Delaware Serial No. 703,155

No Drawing- Applicationbecember 19, 1933,

23 Claims. (01. s-s) I m. invention relates to the m of printing vat dyes on textiles and more particularly to vat dve printing pastes. Specifically, the invention contemplates vat dye printing pastes containinganthraquinone-sulfonic acids and their equivalents.

Except for indigo, vat dyes (which are unlike all other typesof dyes both in properties and mode of application to the fiber) were not known prior to the beginning of the present century.

By .the term vat dyeis meant a colouring matter insoluble in water, but which can be converted on reductiondnto a so-called leuco com-- pound, which is soluble in alkalis, and in such a solution, termed a vat, the actual dyeing procass is eifected; on removing the material from the bath and exposing to the air oxidation takes place, the dye being precipitated on the fibre in insoluble form;

from page 423, of. a Textbook of Dye Chemistry 1 by Georgievics and Grandmougin (1920).

While vat dyes lack desirable afilnity for textile fiber, dyeing, that is coloring of 'the entire .5 fabric (as-distinguished from printing in which only a portion of the fabric 'is colored), with such compounds is relatively simple. The process of dyeing comprises suspending the insoluble chemical compound (vat dye) in an alkaline solution,

and thereafter adding a reducing agent to change the vat dye to its hydro derivative (the reducing agent may; also be added before or simultaneously with thedye) The fiber is then steeped in the solution of the hydro derivative (referred to soon as a sufii cient amount of the leuco body solution has been absorbed. Exposing the soaked fabric to an oxidizing influence, usually the oxy gen of the atmosphere, regenerates the vat dye j on the fiber producing a dyed material.

There is an alternative process known as padding which is used to some extent at'present. According to this process the fiber is immersed in a suspension of a vat dye until a sufilcient quantity of the dye has adheredmechanicallytothe fiber (this adherence is analogous to wet sand; clinging to stick used for stirring a sand and water mixture). Thereafter the fiber with the m dye particles mechanically held thereon,is immersed in an alkaline solution containing a re-' ducing agent whereby the dye particles are re duced to the soluble hydro derivative, penetrate the fiber, and upon removal from the solution followed by oxidation, are regenerated resulting in a dyeing taking placeas in the general process first described. As will be obvious some of the dye is-lostfromthe fiber by reason of going into solution in the vat. If this process is continued long enough, suiilcientdye would be re-- aboveas leuco compound) and is removed as,

moved from the fiber to render the reducing solution a dye vat of ordinary concentration. In-

asmuch as a reduction to the hydro derivative is necessaryboth in dyeing from a solution and by v the padding method, the solution-dyeing process 5 is the one most widely used where space and equipment permit. I

While various reducing agents may be used in the dyeing (as difierentiated from printing) of a vat dyes, the one most commonly utilized is a 10 hydrosulfite.

For some years past solid hydrosulphite of soda, containing amounts of NaaSO4 varying from to per cent., has been in the market 15 in the form of a dry, almost white, powder. It is largely used in the dyeing of indigo and other vat dyes, but, owing to the rapidity with which its solutions oxidize in contact with the air, it is not suitable for textile printing." 20 from page 250 of the Principles and Practice of Textile Printil i by Knecht 8: Fothergill (1924) As indicated in the above quotation, the ordina- I ry reducing agent utilized in the dyeing of vat dyes cannot be used practically in the printing 0! 25 vat dyes on textile. This is a serious disadvantage because vat dyeprinting is, for other reasons, much more complicated than vat dyeing. This particular difilculty has been partially overcome by the discovery and commercial produc- ,which is filled with a printing paste. After leaving the printing machine the printed cloth is quicklypassed into a drier. This dries the print- 5 ing paste on the cloth in its proper place and prevents the dye from spreading to other portions I of the fabric with consequent ruination of the design (in dyeingwith' vat dyes, spreading of the color solution over the entire cloth is earnestly 50 sought for, but in the printing of vat dyes the slightest spreading of the color destroys the value of'the printed cloth to such same is not salable). s

an extent that the as The'printing paste applied to the cloth from the roller is a inaterialthickened to such an ex tent that it does not'run readily. It varies with difier'ent fabrics and manufacturers, but usually consists of a mixture of unreduced vat dye, a strong so reducing, agentsuch as sodium formaldehyde sulfoxylate. an alkali and a thickening agent. The

thickening agent is usually a gum (for instance British gum), starch or both. The printing paste is usually prepared by mixing a dye paste or pastes with the other ingredients enumerated, said other ingredients being in the form of a gummy mixture hereinafter called printing gum". The dye pastes are essentially finely divided suspensions of dye with -or without a dispersing agent. These dye pastes (hereinafter referred to as dye pastes, dyestufi pastes" or color pastes") usually have the dye suspended in water.

In order to complete the printing, the cloth; after leaving-the drier, is passed into an age: (usually a steam ager) for a period of a few minutes, during which time the vat color undergoes reduction (the sodium formaldehyde sulfoxyiate in the printing paste producing its reducing action because of the elevated temperature in the ager) and passes to the fiber. The fabric is then subjected to oxidizing conditions which may include passing it into a steeping bath, usually of water or water containing an oxidizing agent. Any excess color is washed oif in a soap solution with which the textile material is treated following the steeping.

Vat dyes at the time of printing, are not in true solution. For this reason the effecting of complete reduction of the dye and the transfer of the color to the fabric in the brief time which the goods are steamed is a. process accompanied by great dimculties as previously stated. In order .to make sure that satisfactory results are obtained, it is important that the dye paste b'e'of special fineness, but even then a great deal of color is lost because of its failure to dye the cotton. This excess color is washed ofl during the soaplng which follows the steaming.

Because of the aforementioned and other difflcultie's it has previously been proposed to add various chemical substances for convenience called assistants to the printing paste. One such compound is tri-ethanolamine (U. 8. Patent 1,790,950) andwith it markedly improved results have been produced. Another compound which has been proposed for this use-is beta-beta'-dit by the addition of the other customary ingredihydroxy-diethyl-ether (British Patent 368,910)

It is an object of this invention to provide new and improved assistants for the printing of'indigoid dyes. A further object is the production of new and improved indigoid vat dye printing pastes. A more specific object is the production of new and improved thioindigoid vat dye printing pastes. A still further object is the provision of a new and improved printing process. Other objects will appear hereinafter.

These objects are accomplished, according to the present invention, by carrying out the printing of vat dyes of the indigoid type in the presence of an alkali metal anthraquinone-sulfonate. The

alkali metal anthraquinone-sulfonate may be introducedinto the printing paste as such, either separately or as part of the printing gum, or in another suitable manner, or it may be formed in the printinggum or the printing paste, for example,

by reaction of the free sulfonic acid with some of the alkaline reacting agents in the printing gum or printing paste. It may also be added to the dye paste, from which the printing paste is prepared ents, such as for example, the reducing agent, al-

kali and thickening agent. 'It may also beincorporated into the paste in conjunction with other quinone-disulfonic acid,

printing assistants of other types with satisfactory results.

. The invention will be further illustrated but is not limited by the following examples.

Example I A thickener was prepared containing 10% wheat starch, 30% British gum and 60% water.

' From this thickener a printing gum consistingl Per cent Thickener 57.5 Potassium carbonate 16 Sulfoxite 0 (sodium formaldehyde-sulfoxyl- 15 ate) 11' Glycerine 5 Water 10.5

was prepared. 'I'his'printing gum was made into 20 a printing paste by incorporating therein a dye paste of 4 :4 -dimethyl-6 6'-dichloro-thioindigo and anthraquinone-Z-sodium sulfonate. The percentage composition of the printing paste was as follows:

Per cent Printing gum 79.9 Dye paste (12.5% dye) 20. Anthraquinone-Z-sodium sulfonate 0.1

This product was printed on textile material which was then aged and developed in the usual and well known way. The prints obtained were from 10-25% stronger than those obtained from a similar composition which differed only in the omission of the anthraquinone-2-sodium sulfonate. I

In the foregoing procedure, the anthraquinone-2-sodium sulfonate may be substituted by the alkali metal salt of other anthraquinone- 40 sulfonic acids such as, foriexample, 2:6-anthra 2:5-anthraquinone-disulfonic acid, 2:7-anthraquinone-dlsulfonic acid, 1 :B-anthraquinone-disulfonic acid, 1:5-anthraquinone-disulfonic acid, 1:3:6-anthraquinonetrisulfonic acid, 1 z 3 l-anthraquinone-trisuifonic acid, 1-hydroxyanthraquinone-5-suifonlc acid, 1-nitro-anthraquinone-S-sulfOnic acid and 1- chloro-anthraquinone-5 sulfonic acid. The free acids may be used, but it will be recognized that a suitable amount of alkali should be used so that an-adequate amount is present for printing after neutralization of the free sulfonic acid.

' Example I! A printing gum was prepared comprising:

This printing gum was made into a printing pasteby mixing it with a 6:6'-d!ethoxythioindigo (C. I. 1218) dye paste containing 11.5% solids. To this mixture there was added silver salt (the sodium salt of anthraquinone-2-sulfonic Another paste, similar in all respects except that the silver salt was omitted, was prepared and 10 prints made from the two pastes under similar ing paste containing silver salt were. 10-25% stronger than those obtained from the other printing paste.

Instead of silver salt, other anthraquinonesulfonates may be used such as, for example, potassium and/or sodium salts of 2:6-anthraquinone-disulfonic acid, 2:5-anthraquinone-disulfonic acid, 2z7-anthraquinone-disulfonic acid, 1 8-anthraquinone-disulfonic acid, 1 5-anthraquinone-disulfonic acid, 1 :3 G-anthraquinonetrisulfonic acid, 1 :3 7-anthraquinone-trisulfonic acid, 1-hydroxy-anthraquinone-5-sulfonic acid, 1-nitro-anthraquinone-5 sulfonic acid and 1- 25 chloro-anthraquinone-5-sulfonic acid.

Example III A thickener consisting of 10% wheat starch,

30% British gum and 60% water was prepared 30 and made into a printing gum having the following composition:

Per cent Thickener 67.5 .Potassium carbonate 8 35 Sulfoxite C -1 4 Glycerine 5 Water 15.5

A dye paste containing 12% of 6:6'-dimethoxythioindigo and the sodium salt of anthr'aquinone- 2-sulfonic acid were incorporated into the printing gum to produce a printing paste having the following composition:

Per cent Printing gum 79.5 Dye paste 20 Anthraquinone-Z-sodium sulfonate 5 As illustrations of other anthraquinone-sulfonates which may be used to replace all or part 50 of the anthraquinone-Z-sodium sulfonate in the above example, may be mentioned the alkali metal salts of 2:G-anthraquinone-disulfonic acid, 2 S-anthraquinone-disulfonic acid, 2 :7-anthraquinone-disulfonic acid, 1:8-anthraquinone-di- 55 sulfonic acid, 1:S-anthraquinone-disulfonic acid 1 :3 6-anthraquin'0ne -trisulfonio acid, 1:3 :7-anthraquinone-trisulfonic acid, l-hydroxy-anthraquinone-5-sulfonic acid, l-nitro-anthraqu'inone- 6-sulfonic acid and 1-chloro-anthraquinone-5- 60 sulfonic acid.

Example IV A thickener containing 10% wheat starch, 60%

water and 30% British gum was prepared and 65 made into a printing paste having the following percentage composition:

Per cent Thickener 67.5 Potassium carbonate 8 Sulfoxite C 4 Glycerine Water 15.5

This printing gum was made into a printing paste by stirring the same with a 20% dye paste of 5:5'-7:7-tetra-brom-indigo (C. I. 1184, bromiconditions. The prints obtained from the printnation in nitrobenzene) andanthraquinone-2- sodium-suli'onate. After producing a uniform mixture the printing paste, which was composed of:

Per cent 5 Printing gum. 79.5 Dye paste 20 Silver salt 0.5

was printed on cotton, dried, aged and developed 10 in the usual way. The prints obtained were more than 10% strongerthan those obtained from a paste printed under similar conditions which was similar in every respect except that the anthraquinone-2-sodium sulfonatehad been omitted.

Further illustrations of anthraquinone-sulfonates. which may be used to replace all or part of the anthraquinone-Z-sodium sulfonate in the above example are the potassium and/or'sodium salts of 2:6-anthraquinone-disulfonic acid, 2:5- anthraquinone-disulfonic acid, 2:7-anthraquinone-disulfonic acid, 1:S-anthraquinone-disulfonic acid, IrS-anthraquinone-disulfonic acid, 1:3:6- anthraquinone-trisulfonic acid, 1: 3 7-anthraquinone-trisulfonic acid, l-hydroxy-anthraquinone-S-sulfonic acid, l-nitro-anthraquinone-fisulfonic acid and l-chloro-anthraquinone-S-sulfonic acid.

Example V A thickener was prepared including 10% wheat starch, 30% British gum and 60% water. From this thickener a printing gum consisting of:

was prepared. This printing gum was made into a printing paste by incorporating therein a. dye paste of 5:5:7:7'-tetra-br0m-indigo containing 20% solids (C. I. 1184), anthraquinone-2-scdium sulfonate. The percentage composition of the printing paste was as follows:

' Per cent Printing. gum 79.9 Dye paste (20% dye) 20 Anthraquinone-2-sodium sulfonate 0.1

This product was printed on textile material which was then aged and developed in the usual way. The prints obtained were from 10-25% stronger than those obtained from a similar composition which differed only in the omission of the anthraquinone-Z-sodium sulfonate.

Example VI A thickener wasprepared consisting of 10% wheat starch, 30% British gum and the remainder water. This thickener was incorporated in a printing gum having the following composition:

' Per cent Thickener 56.5

-Pota.ssium carbonate 10 Sodium hydroxide 1 Commercial glucose 15 Glycerine 5 Water 12.5

This printing gum was mixed with a 16% (solids) dye paste of bis-beta-naphthio-naphthene indigo and the sodium salt of anthraquinone-beta-sul- Ionic acid to produce a printing paste. This printing paste being composed 01:

Per cent Printing gum 79 Dye paste 20 Anthraquinone-2-sodium suli'onate 1 was printed on cotton textile material in the well known way. Comparison of these prints with prints obtained under similar conditions from a similar printing paste which omitted the anthraquinone-2-sodium sulfonate showed them to be about 15% stronger.

Variations may be made in the type of printing assistant as described, ior instance, in Example Example VII A thickener was prepared consisting of 10% wheat starch, 30% British gum and the remainder This printing gum was with a 16% solids dye paste of 6:6 -dlfluoro-thioindlgo and sodium salt oi. anthraquinone-beta-suliomc acid to produce a printing paste. This printing paste being composed oi:

Per cent Printing gum- 79.1 Dye paste 20 Anthraquinone-Z-sodium sulfonate 0.9

was printed on cotton textile material in the well known way. Comparison with prints obtained under similar conditions from a similar printing pas'te which omitted the anthraquinone-2-sodium sulfonate showed that the (silver salt) paste gave prints about 15% stronger.

Other anthraquinone-sulionates may be employed in carrying out the above procedure instead of the anthraquinone-2-sodium sulionate. The potassium and/or sodium salts of the following anthraquinone-sulionic acids merit special mention: 2:6-anthraquinone-disuli'onic acid, 2:5- anthraquinone-disulfonic acid, 2:l-anthraqulnone-disulfonic acid, 1:8-anthraquincne-disulionic acid, 1:5-anthraquinone-disultonic acid, 1 3:6- anthraquinone-trisuli'onic acid, 1:3:7-anthraquinone-trisuli'onic acid, i-hydroxy-anthraquinone-5'-sulionic acid, 1-nitro-anthraquinone-6- sultonic acid and l-chloro-anthraquinone-5-sul ionic acid.

Example VIII Per cent Thickener 57.5 Potassium carbonate 16 Sodium iormaldehyde-sulfoxylate (Raongalite) 11 Glycerine 5 Water 10.5

was prepared. printing gum was made into a printing paste by incorporating therein anthraquinone-2-sodiumsu1tonate and a dye paste or the dye resulting from condensing 5:l-di-bromisatin chloride with 3-hydroxy-4-methyl-6-chlorothio-naphthene. The percentage composition of the printing paste was as follows:

Per cent Printing gum 79.9 Dye paste dye) 20 5 Anthraquinone-Z-sodium sulionate 0.1

This product was printed on textile material which was then aged and developed in the usual way. The prints obtained were from 10-'25% stronger than those obtained from a similar com- 0 position which difiered only in the omission of the anthraquinone-Z-sodium sulionate.

Example IX The printing paste having the following com- 15 position:

Per cent 5:5 -dichloro-7 :7 -dimethyl-thicindigo dye paste) (C. I. 1209) 20 'Ihickener 55 20 Glycerine 5 Sodium hydrosulflte 5 Sodium hydroxide (36% strength) 5 Sulfoxite C 6 Water 3 Anthraquinone-beta-sodium sulionate 1 was prepared. In the preparation oi. this composition all of the ingredients except the last three mentioned namely, the sulioxite C, water and sllver salt, were brought together, uniformly mixed and heated untfl reduction was complete, whereupon the remaining ingredients were added and the product stirred to uniformity. The thickener in this case consisted of:

I Per cent Of a thickener consisting of: 80

10% wheat starch 30% British gum 60% water Water 3 5 Potassium carbonate 15 This product was printed on textile material 'which was then aged and developed in the usual way. The prints obtained were stronger than those obtained from a similar composition which diflered only in the omission of the anthraquinone-2-sodium sulionate.

In the foregoing example the anthraquinone-2- sodium-sulfonate may be wholly or partly replaced by other alkali metal anthraqulnone-sulfonates, such as for example, the alkali metal anthraquinone-sulfonates of 2:6-anthraquinone-disulionic acid, 2:5-anthraquinone-disulionic acid, 2:7-anthraquinone-disulionic acid. 1:8-anthraquinone-disuli'onic acid, 1:5-anthraquinone-disulionic acid, 1 :3 S-anthraqulnone-trisulfonic acid, 1:3:7-anthraquinone-trisulionic acid, i-hydroxy-anthraquinone-5-sulionic acid, i-nitro-anthraquinone-fi-sulfonic acid and 1-chloro-anthraquinone-5-sulionic acid.

Example X A printing paste was made from the following ingredients: 05

7 Per cent 6:6"- dichloro-thioindigo dye paste (10% solids) 20 Thickener 55 Glycerine 5- NBISQOQ 5 NaOH (36% strength) 5 Sodium formaldehyde sulioxylate (Rongalite) a Water 3 Anthraquinone-2-sodium suli'onate 1 125 The product was printed on textile material. This The method of preparation was as follows; The

dye paste, thickener, glycerine, NazSzO'4 and NaOH were uniformly mixed and heated until reduction was complete. The Rongalite, water and anthraquinone-2-sodium, sulfonate were thereafter added. The product was stirred to uniformity. The thickener used was:

I I Per cent Of a composition comprising: 80 1o wheat 1 30% British'guin' 60% water a Water I 5 KzCOa was aged and developed as usual. The prints were 10-25% stronger than those .made with a similar composition from which the anthraquinone-2-sodium-sulfonate had-been omitted.

Erample XI The following ingredients were incorporated into a printing .paste:

2r Percent 5:5 difiuoro thioindigo dye paste (10% solids) 20 Thickener 55 Glycerine 5 N8aS2O4 -Q ,5 NaOH (36% strength) 5 Sodium formaldehyde sulfoxylate (Rongalite) 6 Water I I 3 Anthraquinone-2-sodium sulfonate 1 The dye, thickener, 'glycerine, Na:S-.-O4 and NaOH were brought together and uniformly mixed.

Heat was applied until reduction was complete.

Then the Rongalite, water and anthraquinone-Z- sodium sulfonate were added. The product was stirred to uniformity.

The thickener used was prepared as'follows: 7

Into a composition consisting of 10% wheat starch, 30% British gum. and 60% water, there was stirred K200: and H20 until the resultant material was as follows: 7

Per cent Composition 80 Water 5 KzCOa 15 The printing paste obtained was printed on a T I textile material and aged and developed-as usual.

These prints were from iii-25% stronger than a corresponding paste without the silversalt.

Erample XII A printing paste of the following composition was prepared:

f Percent 4:4'-dichloro 5:5 di bromo indigo (C. I.

1189) (20% solid dye paste) 20 Thickener 55 Glycerine 5 5 N32S2O4 5 NaOH (36% strength) 5 Sodium formaldehyde sulfoxylate 6 Water Anthraquinone-Z-sodium sulfonate 1 70 The .method useddn preparation was this: The dye v paste, thickener, ,glycerine, NaaSaO; and NaOI-I were uniformly mixed and heated to complete reduction. 'I'hCa sulfoxyl'ate, water and, an- ,thraquinone sulfonate were added. This product 75 was .stirred.to;.uniformity. The thickener used was made by mixing 10% wheat starch, 30% Brit- -ish gum and 60% water and to 80% of such com- :DOSltlOll adding 5% waterand 15 potassium carbonata. when the productwasprinted on a textile material, agedanddeveloped, the prints were 5 found to be Iii-25% stronger than those made without any anthraquinonee2- sodium sulfonate.

This printing gum was mixedwith a 12.5% color paste of 4:4'.-dimethyl-6:'6-dichloro-thioindigo and sodium salt of anthraquinone-beta-sulfonic 5 acid to produce a printing paste. This printing paste, being composed of: I

. Per cent Printing gu '79 Dye paste 20 3 Anthraquinone-2-sodium sulfonate 1 was printed on cotton textile material in the well known way. Comparison with prints obtained under -similar conditions from a similar printing paste which omitted the silver salt, showed about 35 20% I greater strength in the-print from the printing paste of this invention,

Variations may be made in the type of anthraquinone-sulfonate employed as the printing assistant. Thus, all or a part of the anthraquinone- 2-sodium-s'ulfonate may be replaced by the alka- -li metal salts of am of the following anthraquinone-sulfonic acids or mixtures thereof: 2':6-anthraquinone-disulfonic acid, 2:5-anthraquinonedisulfonic acid, 2: 7 anthraquinone-disulfonic acid, 1:8-anthraquinone-disulfonic acid, 1:5-anthraquinone-disulfonic acid, 1 :3 fi-anthraquinone-trisulfonic acid, 1 :3 7-anthraquinone-trisulfonic acid, l-hydroiw-anthraquinone-fi-sulfonic acid, I-nitro-anthriaquinone-G-sulfonic acid and 50 1-chloro-anthraquinone 5-sulfonic acid.

Example XIV A thickener was prepared containing 10% 55 wheat starch, 30% British gum and the remainder water. This thickener was incorporated in a printing gum having the following composition:

- Per cent 60 Thickener 56.5 Potassium carbonate 10 Sodium hydro 1 Commercial glucose 15 Glycerine r 5 Water. 12.5

This printing gum was mixed with a 20% solids dye paste of 5:5'-di-brom-'1:7'-dimethyl-thioindigo and anthraquinone-beta-sulfonic acid to produce a printing paste. This printing paste being composed of Percent Printing gum I H 79 Dveim e' Y 20 'An r quin n -zrsu i +;-;+-+.-e- 1 known way. The prints obtained under similar conditions from a similiar printing paste which omitted the anthraquinone-2-sodium sulionate were about 15% weaker.

was prepared. In the preparation of this composition all or the ingredients except the commercial glucose, water and silver salt were added, uniiormly mixed and heated until reduction was completewhereupon the remaining ingredients listed were added and the product stirred to uniiormity. The thickener in this case consisted of: 7

Per cent Water 58 Wheat star 8 Potassium carbonate 15 British gum 24 This product was printed on textile material which was then aged and developed in the usual way. The prints obtained were from 10-25% stronger than those obtained from a similar composition which diiiered only in the omission o! the silver salt.

' Example XVI The printing paste having the following composition:

Per cent 0! a dye paste of the thioindigo dye prepared by well known methods from 2-'thiog1ycol naphthalene (14% solids) 20 'I'hickener Glycerine 5 Sodium'hydrosulflte 5 Sodium hydroxide (36% strength) 5 Commercial glucose 9 Anthraquinone-beta-sodium sulionate 1 was prepared. In the preparation of this composition all of the ingredients except the commercial glucose, water and anthraquinone-betasodium sultonate were added, uniformly mixed and heated until reduction was complete whereupon the remaining ingredients were added and the product stirred to uniformity. The thickener in this case consisted 01:

Per cent Water 53 Wheat star h 8 Potassium carbonate 15 British g 24 This product was printed on textile material which was then aged and developed in the usual way. The prints obtained were from 10-25% stronger than those obtained from a similar composition which diiiered only in the omission of the anthraquinone-2-sodium sulionate'.

was printed on cotton textile material in the well Example XVII The printing paste having the following composition: g

Per cent Of a dye paste 0! the dye resulting from condensing 5:7-di-brom-isatin chloride with 3-hydroxy-4 methyl-6 chloro-thio-naphthalene (10% solids) 20 Thickener 55 Giycerine 5 Sodium hydrosulfite 5 Sodium hydroxide (36% strength) 5 Commercial glucose 9 Anthraquinone-Z-sodium sulionate 1 15 was prepared. In'the preparation of this composition all of the ingredients except the glucose. water and silver salt were added, uniformly mixed and heated until reduction was complete whereupon the remaining ingredients were added and theproduct stirred to uniformity. The thickener in this case consisted oi:

Per cent Water 5s Wheat star h 8 Potassium carbonate 15 British g 24 This product was printed on textile material 30 which was then aged and developed in the usual way. The prints obtained were from 10-25% stronger than those obtained from a similar composition which differed only in the omission of My the silver salt.

Example XVIII The printing paste having the following com- 40) position:

. Per cent 6:6'-diethoxy thioindigo (C. I. 1218) (11.5%

solids dye paste) .20 45 'Ihickener 55 Glycerine 5 Sodium hydrosulflte 5 Sodium hydroxide (36% strength) 5- Commercial glucose 9km;

Silver salt..

was prepared. In the preparation 0! this composition all of the ingredients except the commercial-i glucose, water and silver salt were added, uni- 5m formly mixed and heated until reduction was. complete whereupon the remaining ingredients were added and the product stirred to uniformity. The thickener in this case consisted oi:

(ill) Per cent Water 53 Wheat star h 8 Potassium carbonate 15 British gum 24 This product was printed on textile material which was then aged and developed in the usual way. The prints obtained were from 10-25% stronger than those obtained from a similar composition which diilered only in the omission of the silver salt.

The variations as to the type of printing assis ant may be similar to those given in connection with Example XIII.

Example XIX The printing paste having the following composition:

was prepared. In the preparation of this com-- position all of the ingredients except the glucose, water and anthraquinone-beta-sodium sulfonate were added, uniformly mixed and heated until reduction was complete whereupon the remaining ingredients were added and the product stirred to uniformity. The thickener in this case consisted of:

Per cent Water 53 Wheat starch 8 Potassium carbonate 15 British gum 24 This product was printed on textile material which was then aged and developed in the usual way. The prints obtained were from 10-25% stronger than those obtained from a similar composition which diii'ered only in the omission of the anthraquinone-beta-sodium sulfonate.

Example XX A printing gum was prepared from:

Per cent Thickener 57. 5 K200: 16 Bulioxite C 11 Glycerine 5 Water 10 The thickener contained 10% wheat starch, 30% British Gum and 60% water. A printing paste was made from the printing gum by adding 6:6-

diethoxy-thioindigo (C. I. 1218) dye paste containing 11.5% solids. To this mixture was added milled silver salt (sodium salt of anthraquinone- 2-sulionic acid). ,The resulting printing paste had the following composition:

Per cent Printing g 79. 9 Dye paste 20 Milled silver salt 0. 1

Two other pastes were prepared, similar in-all respects except that in one the silver salt was not milled and in the other the silver salt was omitted. Prints were made from the three pastes under similar conditions. .The prints made from the two printing pastes containing the silver salt were l0-25% stronger than those made from the paste from which silver salt was omitted. But it is also worthyoi notice that those prints made from the paste containing the milled silver salt were noticeably stronger than those printed with the paste containing silver salt whichjhad not been milled. I

As further illustrations of alkali metal anthraquinone-sulionates which may be used to replace in which the sulfonic acids and mixtures thereof: 2:6-anthraquinone-disulfonic acid, 2:5-anthraquinone-disulionic acid, 2:7-anthraquinone-disulionic acid,

1 8-anthraquinone-disulionic acid, 1 5-anthraquinone-disulfonic acid, 1:3:6-anthraquinone- 5 trisulfonic acid, 1 3 'I-anthraquinone-trisulfonic acid, l-hydroxy-anthraquinone-S-sulionic acid, 1-nitro-anthraquinone-6-sulfonic acid and 1- chloro-anthraquinone-5-sulionic acid.

10 Example XXI A printing gum was made from:

1 Per cent Thickener 67. 5 15 K200: 8 Sulf0xite C 4 Glycerine 5 Water 15. 5

The thickener contained 10% wheat starch, 30% British gum and 60% water. This printing gum was used to make a printing paste by mixing uniformly .with a dye paste containing 12.5% of 4:4'-dimetlurl-6:6' dichloro thioindigo and a 25 small amount of milled silver salt. The following proportions were present in the finished composition:

Per cent Printing gum 79.9 30 Dye paste- .L 20 Milled silver salt --.i. 0.1

Prints made from this printing paste were 10-25% stronger than those made from a similar paste in which silver salt was absent, and noticeably 35 stronger than those made from a similar paste which contained silver salt which had not undergone the milling process.

The thickener contained 10% wheat starch, 30% British gum and 60% water. A printing paste was made from this gum by mixing uniformly with a. 16% solids dye paste oi bis-beta-naphthio- 55 naphthene indigo, and the milled sodium salt of anthraquinone-beta-sulionic acid in the following proportions:

Per cent Printing gum 79 Dye past 20 Milled anthraquinone-beta-sodium sultonatel Prints were made from this paste. These prints were compared with prints made from a similar paste which lacked the presence oi'the milled assistant. The prints from the paste with the milled silver salt assistant were 10-25% stronger than the others. They were also noticeably stronger than prints made from a similar paste silver salt assistant used was not milled.

The type 01' anthraquinone-sulionate may be varied, as for example, according to the variations given in Example xx.

The composition of the thickener'herein utilized was 10% wheat starch, 30% British gum and 60% water. This printing gum was made into a printing paste with a 5:5-dichloro-6:6'-dimethyl thioindigo dye paste containing anthraquinone-2- sulfonic acid. The composition of the printing paste was:

Per cent Printing gum 79 Color paste (12.5% dye solids) 20 Anthraquinone-2-sulfonic acid 1 This paste gave prints several percent stronger than a similar paste not containing anthraquinone-2-sulfonic acid when printed, dried, aged and developed in the usual way.

Example XXIV A thickener whose composition was 10% wheat starch, 30% British gum and 60% water, was incorporated into a printing gum whose composition was Per cent Thickener 57.5 Sodium formaldehyde sulfoxylate ll Glycerine 5 Water 10.5

This printinggum was made into a printing paste by mixing the same with appropriate quantitles of a 20% dye paste of 5:5-dichloro-7:7'- di-bromo-indigo and a water suspension of anthraquinone-2-sodium sulf'onate which had been milled in water. The composition of the resulting printing paste was as follows:

, Per cent Printing gum 19.9 Color paste 20 Anthraquinone-2-sodlum sulfonate 0.1

It is to be understood that the invention is not limited to the specific dyes listed in the above examples. Other indigoid dyes are well known to those skilled in the art and are disclosed in suc publications as:

1. Technologie der Textilefasern Kiinstliche Organische Fabstofie H. E. Fierz-David 2. Color Index (1924) Supplement (1928) Society of Dyers and Colourists 3. Fortschritte der Teerfarben -Fabrikation P. Friedlaender 4-. Farbstoiftabellen Gustav Schultz (1931) 5. Enzyklopadie der Kiipenfabstoii'e Truttwin Specific mention may be made of such other compounds as 2:3:2':3'-di-anthraquinone indigo, bromo-2-beta-naphthindol-2-indol indigo,

indigo, thioindigo, 2-(5z'l-di-brom-indol) -2'- an-' thracene indigo, 2-(5z7-di-brom-indol) -2'-naphthalene indigo, 4:4'-diethyl-thioindigo, 5:5'-dimethyl bis thionaphthene indigo, bis-alphanaphindol indigo, 4:5:6:7:4':5':6':7-octo-ch1oro-indigo, dimethyl-indirubin, dibrom-indirubiri, dyes prepared by the condensation of reactive 2- isatin derivatives with naphtho-carbamle bodies (e. g. ortho tolu 5 hydroxy alpha naphthocarbazole), indol-acenaphthene indigoes, thio- 5 naphthene-indolindigoes, and the like. The specific dyes of U. S. Patents 1,558,252 and 1,792,648 also merit particular mention.

Where a mixture of alkali metal anthraquinone-sulfonates is used, it may be such as is 10 obtainable from a residue resulting from the sulfonation of anthraquinone after the removal of anthraquinone-Z-sulfonic acid. The ammonium salts of the various anthraquinone-suli'onic acids are usually considered to be equivalent to the 15 alkali metal salts, insofar as chemical'action is concerned, although in some cases the results may not be as satisfactory, particularly where the decomposition of the salt with the liberation of ammonia occurs.

The amount of the assistant is ordinarily varied directly with the amount of solid -dyestufl and the paste used based on a 12.5% solids dye paste. The preferred amounts of the printing assistant are about 1 to about 5%. Greater or smaller 25 amounts than this may be used when desired. For example, the use of .5 to 10% of the printing assistant gives good results. Less than .5% may be used if desired, although the result is not as noticeable as that produced by using an amount 30 falling within the preferred range. ,Generally, more than 10% may be used without detriment to the process.

As previously indicated, all types of reducing agents are not suitable for printing. This is well 35 recognized by those skilled in the art, and it will be understood, therefore, that the term reducing agent" as herein used in conjunction with print-' ing pastes, is an agent which is suitable for vat dye printing. Sodium formaldehyde-sulfoxylate 40 is a material well adapted for printing vat dyes, inasmuch as it is not oxidized at ordinary tem-' peratures and exercises its reducing action at elevat'ed temperatures.

This invention is of great importance technical- 45 ly and commercially, since it has been found that the presence of assistants of the types described in indigoid printing pastes, and particularly in the printing of thioindigoid dyes, makes possible the production of prints of superior strength and 50 brightness to those obtained from a similar printing paste from which the assistant has been omitted. 1

So much of this application as relates to printing with unsubstituted anthraquinone sulfonic 55 acid and sulfonates is claimed in our co-pending application Serial No. 504,274 filed December 23. 1930, of which the present application is a continuation'-in-part. The specific embodiment of the invention relating to printing with anthra- 0 quinone-2-sulfonic acid and salts thereof is claimed in our U. S. application Serial No. 703,156 filed December 19, 1933.

As many apparentlywidely diiferent embodiments of this invention may be made without de- 55 parting from the spirit and scope thereof, it is to be understood that we do-not limit ourselves to the specific embodiments thereof except as defined in the following claims.

We claim:

1. A vat dye printing paste comprising an metal anthraquinone-sulfonate.

2. An indigoid vat dye printing paste comprising an alkali metal anthraquinone-sulfonate.

3. A printing paste comprising a thioindigoid 7 dye and an alkali metal anthraquinone sulfonate. 4. A printing paste comprising a thioindigoid dye and an anthraquinone-sodium-sulfonate.

' 5. A printing paste comprising 4:4'-dlmethy1- 6:6-dichloro-thioindigo and an alkali metal anthraquinone-sulfonate.

6. A printing paste comprising 6:6'-diethoxythioindigo and an alkali metal anthraquinonesulfonate.

7. An indigoid printing gum comprising an alkali metal anthraquinone-sulfonate.

8. A thioindigoid printing gum comprising an alkali metal anthraquinone-sulfonate.

9. The process of printing indigoid dyes which comprises applyinglto the fiber a printing paste comprising the indigoid dye, an alkali metal salt of an anthraquinone sulfonic acid, printing gum, alkali and a reducing agent suitable for printing, and thereafter drying, aging and developing the print.

10. In the process of printing indigoid vat dyes on textiles, the step which comprises incorporating a substance selected from the class consisting of anthraquinone-sulfonic acids and an alkali metal salts thereof into the printing paste.

7 11. In the process of printing thioindigoid vat dyes on textiles, the step which comprises incorporating a substance selected from the class consisting of anthraquinone-sulfonic acids and an alkali metal salts thereof into the printing paste.

12. In the printing of textile material, the step of printing on the textile material with a printing paste comprising an indigoid vat dye and an alkali metal anthraquinone-sulfonate.

13. The process of printing thioindigoid dyes which comprises applying to the fiber a printing paste comprising the thioindigoid dye, an alkali metal salt oi an anthraquinone-sulfonic acid, printing gum, alkali and a reducing agent suitable for'printing, and thereafter drying, aging and developing the print.

14. The process of printing thioindigoid dyes which comprises applying to the fiber a printing paste comprising a thioindigoid dye, an alkali metal salt of an anthraquinone-sulfonic acid, printing gum, potash and sodium formaldehydesulfoxylateand thereafter drying, aging and developing the print.

g 15. The method of printing with vat dyes of the indigoidtype which comprises applying to the goods a composition containing the indigoid dye, a reducing agent suitable for printing, an 10 alkali metal salt of an anthraquinone sulfonic acid'and an alkali metal carbonate, ageing the same in steam and reoxidizing in a developer.

16. A vat dymprinting paste comprising a water-soluble polyhydric alcohol and an alkali metal anthraquinone sulfonate.

17. A printing paste comprising a thioindigoid dye, 'glycerine, and an alkali metal anthraquinone sulfonate.

18. A thioindigoid printing paste comprising a water-insoluble thioindigoid color, a printing gum and from about 0.1 to about 1.0% of an alkali metal anthraquinone sulfonate.

19. A printing paste comprising a water-insoluble thioindigoid color and an alkali metal hydroxy anthraquinone sulfonate.

20. A printing paste comprising a water-insoluble thioindigoid color and an alkali metal chloro-anthraquinone sulfonate.

21. A printing'paste comprising a water-insoluble thioindigoid color and an alkali metal nitro-anthraquinone sulfona 22.'The process of preparing printed materials which comprises printing on a textile material with 4:4'-dimethyl-6:6'-dichloro thioindigo in the presence of an alkali metal anthraquinone sulfonate.

23. The process of preparing printed materials which comprises printing on a textile material with 6:6'-diethoxy thioindigo in the presence of 40 an alkali metal anthraquinone sulfonate.

HERBERT A. LUBS. JOHN ELTON COLE.

CERTIFICATE OF CORRECTION.

Patent No. 2,024,974. I v December 17, 19:55.

HERBERT A. LUBS, ET AL.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Page 2, first column, line 1, strike out the comma after "reducing" and insert the same after "agent" in same line; page 6, second column, line 9, for the syllable "thalene" read thene; and that the said Letters Patent should be read with these corrections therein that the same may conform to the record of the case in the Patent Office. I I

Signed and sealed this 11th day of February, A. D. 1936.

Leslie Frazer 7 Acting Commissioner of Patents. 

